Process for separation of vapors



May 1, 1945.

T. w. EVANS ETAL 2,374,984 PROCESS FOR SEPARATION OF VAPORS Filed Jan. 12. 1942 Invznforsfihzodorz W. Evans Rupczfl C. Morris Patented May 1, 1945 rnocsss son sum-nos or varoas Theodore w. Evans, Oakland, and Rupert 0.

Morris, Berkeley,

velopment Company, 8

an corporation of Delaware minors to Shell De- Franoisco, Calif., a

Applications-ma a, 1942, Serial No. 420,442; Claims.. (cuss-11s) This application is a continuation-in-part of our co-pending application, Serial No. 329,482, filed April 13, 1940, and the invention relates to a process for the separation, or purification, or both, of vapor mixture of narrow boiling range comprising two or more' components of different chemical compositions, by contacting such a vapor mixture with a higher boiling liquid which has a preferential solvent power for-certain of the components to be separated. More particularly, it deals with a method for scrubbing vapor mixtures with a suitable selective solvent for one component and refluxing the resulting fat solution under substantially iso-. thermal conditions, with vapors of the substantially pure component of preferential solubility.

Various methods for separating vapor mixtures of narrow boiling ranges are known. For example, the scrubbing of the vapors to be separated with a selective solvent for certain constituents, in a suitable contact zone such as a packed, spray or bubble plate tower, has long been employed. Several improvements over simple scrubbing have led to the so-called extractive distillation" in which a selective solvent for certain of the components of the vapor mixture is allowed to run down a distillation column as the mixture is fractionally distilled. The more soluble components of the vapor are withdrawn from the bottom of the still in solution in the solvent from which they can usually be readily separated, while the less soluble vapors,

go overhead.

In the extractive distillation there is at the bottom of the column a heat source which causes vaporization of at least a portion of the extracted components. The resulting vapors rise through the lower portion of the column in countercurrent to the descending liquid, thereby displacing from the liquid dissolved components of lower solubility, the latter eventually being withdrawn from the top of the column as undissolved vapors.

It is an object of our invention to provide a process for the separation of gaseous mixtures Separations of this sort are dependent upon the relative volatilities of substances to be separated. The term relative volatility" as used herein is defined for a two component system in the presence of a higher boiling selective solvent as follows:

=5 1 x, X, wherein It is known that the relative volatilities of substances are a direct measure of the ease of their separation by distillation processes. Relative volatilities vary with temperature, and for most mixtures there exists a temperature atwhich this relationship is most favorable for complete separation. In operating an ordinary extracby vapor phase extraction into at least two comnonent fractions with the aid of a higher boiling selective solvent for one or more of the components. which process is more efllcient than similar known processes. It is a further object to provide a means which allows uniform and precise control of fractionation and selective absorption, and it is a still further object to increase the efficiency of selectivevapor or gas absorbing and rectifying apparatus.

' near that which gives tive distillation there is a temperature gradient throughout the length of the contact zone. Since optimum relative volatilities exist at one temperature only it is therefore possibleto take advantage of this optimum relative volatility at only one point in the zone.

Our invention corrects these difliculties and comprises a method similar to extractive distillation but differing therefrom in the maintenance of substantially uniform temperature throughout the length of the contact zone. This weachieve by contacting a vapor mixture of narrow boiling range with a selective solvent for certain components of the mixture at ,a uniform temperature, preferably above the dew point of the feed, to produce a fat solution and then further contacting the latter at about the same temperature with a vapor consisting of the substantially pure component of the mixture which is preferentially soluble in the solvent. Overhead vapors are con'densed to provide liquid reflux, which is returned to the system as described below. We prefer to operate at a temperature the most favorable relative v latility, which can be determined experi- V entally for any given mixture in the presence of! various selective solvents.

The temperature of most favorable relative olatility varies for diflerent solvents and differnt vapor mixtures to be separated. If it is ecessary that this optimum temperature be known accurately, it must be determined experimentally for each combina Normally it is several degree e. I-. about 5 to 26 6., above the dew point oi the reflux. Selectivity of the solvent is one of the factors determining it, and absolute solubility of the vapors in the solvent is another. In general, solubility of vapors in liquids increases with a lowering of the temperature. Selectivity may increase or decrease with temperature, depending for example on the nature of the solvent. In many cases, the selectivity increases as the concentration of dissolved material decreases, so greatest selectivity is reached coincident with no solute in solution, corresponding to an infinite consumption of solvent per pound of product. Therefore, lowering of the temperature may have an adverse eifect on the resulting relative volatility of the several components contained in the vapor mixture, and in practice one must strike a balance between selectivity and solubility. Moreover, pressure must be taken into consideration, since solubility of gases in liquids increases with pressure. In general, increasing the pressure adverselv atl'ects selectiviiw of the solvent.

Some solvents, particularly those which form loose addition compounds with one component of the mixture, show an anomalous increase in selectivity with lowering of the temperature, or with change in pressure, or both. This increase may be so great as to overshadow all other infiuences. when operating our process with such a solvent it may be desirable to maintain a temperature as low as possible without causing actual condensation of the feed, 1. e., to operate as close as possible to the initial condensation point of the vapor mixture. An example of the separation of a vapor mixture which is advantageously carried out at the lowest practical temperature is the separation of diolefines from hydrocarbon mixtures with the aid of cuprous chloride solutions in water or amino bases.

One of the advantages of our isothermal mode of operation may be concluded from the followin explanation. If two columns are compared, to which a selective solvent is admitted to the top, one an ordinary extractive distillation column which is operated at a lower temperature at the top than at the bottom, and the other a column which is operating by maintaining a uniform temperature (which is an average between the top and bottom of the first throughout the length of the column), the following distinctions may be noted. In the first column, as compared to the second, by reason of the lower top temperature in the former, and the fact that even a selective" solvent dissolves appreciable quantities of the less soluble component, it is found that a greater portion of the component having the higher volatility is dissolved by the selective solvent. The addition to the solvent of this component alters and normally lowers its selectivity so that it would tend to dissolve proportionately larger amounts of said less soluble compound. Consequently the selective absorption for the more soluble component would be reduced, and in extreme cases might even be below that of the other component in this portion of the column. Thus the component having the lower relative volatility would tend to pass up the column unabsorbed and contaminate the top product. This detrimental condition is not so pronounced in the second column because, other things being equal, its top temperature is higher than that of the first column, with the ratio of the solvent to Bil iii

absorbed component (which reduces the selectivity of the solvent) remaining high.

By substantially uniform temperature we mean that uniformity which can be maintained readily by employing conventional temperature control means. The degree of temperature uniformity that can be attained in any given apparatus depends of course upon its size and the precision of the temperature control instruments available. It may be said that ordinarily large installations are often somewhat more diillcult to control precisely than small ones, but in general we prefer to operate in such a manner that the temperature fluctuations are held to a minimum and do not vary more than about 5 C. between any two points in both of the contact zones.

Our process will be more fully understood from the drawing. which represents a flow diagram of one embodiment thereof involving two variations. For purposes of illustration, a vapor feed consisting of two components, A and B, having approximately the same boiling temperatures, is to be separated, A being more soluble than B in a relatively high boiling selective solvent 8. Thus,

the solubility of A in S the solubility of B in S The first variation, in which lean solvent is mixed with reflux from the condensed overhead vapors and the mixture returned to the contact column, may be illustrated as follows:

The feed, comprising components A and B, is admitted via line I to the scrubbing section of the contact column 2 comprising that portion of contact column 2 between the feed port at l and solvent port at 3. Column 2 may be a spray, packed or bubble plate tower. In the scrubbing section the feed comes in contact with the solvent S, the solvent preferably being already saturated with component B. The solvent 8 is admitted to the upper portion of column 2 via line 3. As the solvent flows down through the column it comes in contact with ascending vapor mixture, dissolving component A, which at the same time displaces some of component B. Excess component B rises to the top of column 2 and is removed through vapor line 4, and a portion is withdrawn through valved line 2|, as product.

The resulting fat solvent further flows down through the lower rectifying portion of column 2 below the feed port at I, wherein it is further contacted with an amount of relatively pure vaporous component A, which is admitted to the bottom of column 2, via line 5, to serve as stripping agent to displace from the solvent B whatever component B it may still contain. The amount of component A admitted to the bottom or column 2 should not be more than that which will completely dissolve in solvent S under the conditions of the extraction and should, at the same time, not be less than that amount which will displace a major portion and preferably all of component B from the solvent. Thus, fat solvent S leaves the bottom of column 2 containing substantially only dissolved component A via line 8 and is transferred to iractionating column 1 which is equipped with reboiler 8 and partial condenser 9, the latter for producing reflux. From this fractionating column a vapor stream of substantially pure component A passes overhead and is divided into two portions, one portion recycling through line It, temperature regulator ii and line 5 to the bottom of contact column 2, and the remaining portion being withdrawn aerated it the'desired' operating temperature as possible.

8 M the system thl'OlllhJlllQjlI-O In thehleribed drawing. simplified embodishown. f mentsor-ourinvantionhavebeenshownand it or'fractionatln column thromiiv is that variations with respect to line liandvalvedline ll (valveil-lieila'elos'edl tbepl'aosment orapparawsm h mn ra m toeocler llandaccumulator I'l Deregulators, valves, by-passes, etc., can be made Y fore entering ccolerlo the lean solvent and a without departing from the spirit of our invenportionorcomponentnarecombinedthew, tion."lbel o9erplacementofpumpsandother m lncmixturep saingtocool vla ne 'auxiliarleswillbeevidenttooneskilledinthe andvalvedlineis (valves llandllbeingpropart. erly regulated). In cooler II. B is condensed to Examples of mixtures which may be advaniorm atrueliuuid Valv s 0. I. ar closed tageously fractionated by our process are coke and the mixture or solvent and condensed confoven gas, low boilin liquid or gaseous hydroponent B is returned to contact column 2 via lines -n of mind m petroleum products ll and 8 for use in m h r 7 b01118 such as gasolines or preferably narrow boiling open). The auid component B 18 returned to fractions thereof, vaporous mixtures of various the column as reflux to aid in the separation of isomeric compounds, constant boiling vapor mixcompcnents A and B. tures, etc. Our process is particularly applicable In the second variati n of our p the 19m to the separation of substances of different desolvent is not presa ra with 60mm! grees of saturation having substantially the same head vapors. This m d 1' p -9 51mm 20 boiling range, for example the separation of butato the manner above described, except lean diene from butylenes and butanes, or butylenes Solv nt M f the bottom 0! column 7 from butane, or propylene from propane. It can through valved ine II (valves 11 and also be suitably employed for the separation of ing closed) thmllshlempelffltul'e regulatm' compounds or different degrees of aromaticlty and lines I! and 3 back to 60mm? column such asinthe separation of toluene from suitable Valve II is closed and the overhead vapors of narrow boiling gasoline fractions, or in the sepacomponentB peastococ e onde se ush ration of gasoline into fractions 01 higher and line 4 and valved line I. and condenled'vflpol's lower octane numbers. It may be employed in collect in accumulator a Po retllmlnfl desuliurization processes in which gasolines of to contact column 2 via line 20 and valved line reduced sulfur content are produced with the aid is as reflux. pondensed B is withdrawn'through of solvents which selectively extract the sulfur valved line II as product. In thi mode of D compounds; and it may also be used in the detion the liq i refi "W to Scrub Solvent from hydration of alcohols, ketones, formic acid, acetic the overhead vapors in the porti of thecolllmn acid and other organic compounds with the aid 1 above the solvent port at of solvents preferentially dissolving the organic A8 P inted out before. it is essential o the Pe compound and having boiling temperatures subationof our process that a substantially stantially above the operating temperature. form temperature be maintained throughout In general our process is not limited to treatcolumn 2 below the o n feed D011; t ment of vapors of substances which exist as mally the temperature at th top P i f 811 40 vapors under normal conditions of temperature ordinary distillation column. e. 8-. th mp and pressure. When it is desired to treat subture on the top tray (that is, that portion correstances which are liquids at ordinary temperasponding to the level of contact column 2 at the tures, it is possible either to vaporize them before solvent reed port at 3 is maintained ppr xithey enter the contact zone or to feed them as o at the dew oint of the reflux. Inasmuch liquids to the contact zone in which latter case as h p m extraction temperature is 8 they become vapors within the zone. When ally higher thanthis dew point. isothermal operfeeding liquids, it is usually advantageous to ation differs from normal operation in that a supply a heating coil at the point where the feed higher than normal temperature is maintained enters the contact zone to prevent local cooling in the top of the column. This may be eifected and thus better to maintain the temperature by surrounding this column with jacket 22 to uniform throughout the length of the contact which is supplied a heat convection medium such zon as wa e oil. naph al n inh ny dip eny Depending on the mixtures to be separated. oxi e. et s heir v to B n. mil n ain- 5 diilerent solvents may be employed. For exing the temperature mif m n at the proper ample. in the recovery of dioleflnes irom oleiines. level throughout the len th i the c l mn- Th the following solvents, which are selective for the convection medium can be heated as liquid or diolennes; are suitable: nitromethane, iuriural, vapor in temperature regulator 23. and be ciracetone, methyl ethyl ketone, dioxane, acetoniculated through jacket 22 via lines fl and II. 0 trile, solutions of cuprous chloride in water .or The choice of substances used as a convection aliphatic amines, etc. If desired, the solvent may medi m epends upon the temperature at which be one which is more selective for the more satuthe contact zone is to be operated. The jacket ilrated hydrocarbons, e. g., cyclohexane, higher lustrated is especially useful when it is desired paraflin petroleum oils, etc. In the separation to operate this column at temperatures subto oi toluene from gasoline or in the desulfurization stantially above atmospheric. or alkyl phenols, furi'ural, aniline. nitrobenzene, If desired. heating or cooling means not shown. beta-beta'-dichlorethyl ether, ethyl carbitol, etc., such as coils, may be inserted within the column maybe employed. I at appropriate points. Such coils may pple- While the amount of solvent employed in our ment or be substituted for the jacket 22. It is '7" process will vary with the particular requirements further highly desirable that the temperature of for any given case. in general we prefer to use the three streams entering column I via lines enough solvent to dissolve a major portion of the I, 8, i and 21, respectively, be accurately conconstituent to be extracted, but not substantially trolled and bemaintained preferably no close to 7 more than is necessary for this. The proper a amount for an individual case can be easily determined by simple experiments. In general, any solvent may be employed in our process which has greater solvent power for at least one of the constituents oi the vapormixture which is to be separated, which has a boiling temperature high enough so that it can be readily separated by fractional distillation from the dissolved lower boiling constituent and whichis chemically and ther- Ex mple A mixture of 39% butadiene, 19.7% isobutylene, 39.9% n-butylenes, 1.4% saturates, presumably butane, in the vapor state, was countercurrently extracted in a forty-plate extraction column with a solution of 20% water and 80% acetone. The butadiene feed mixture entered the column about one-third the distance from the top. Overhead vapors were condensed by contact with returned solvent and the resulting reflux admitted to the column along with the solvent. Isothermal operation was compared with extractive distillation under the conditions described below. The vapors of the feed and the solvent in the isothermal operation were maintained at the same temperature, the column being jacketed by. a recirculating water jacket. In the extractive distillation, no jacket was used. The pressures maintained in ,both runs were substantially atmospheric.

Extractive distillation Column temperature top........ 0.. 14 5.4 Column temperature bottom. 14 16.4 Solvent feed rate .cc. min.. 22 22 Pounds of solvent per pound of cod. 24 24 Feed rstc ..cc./min.. 300 300 Reflux ratio (solvent free basis)... 15:1 15:1

The analysis of the products follows:

The above data show that the isothermal operation is considerably more efllcient, only 1.8% butadiene being lost in top products as compared to 7.1% in the case of extractive distillation under otherwise identical conditions.

,We claim as our invention:

1. In a process for frsctionating a relatively narrow boiling vapor mixture comprising components of greater and lesser solubility in a selective liquid solventin an extraction system, the steps comprising contacting said mixture in the vapor phase with said liquid solvent in a flrst contact zone wherein said solvent dissolves preferentially at least a portion of said component of greater solubility as well as the lesser portion of said component of lesser solubility, under conditions to take overhead undissolved vapors, condensing at least aportion of said overhead vapors. and returning condensed vapors to s'ild extraction system as reflux, passing thairesulting solvent through a second contact zone wherein it is contacted with substantially pure vapors of said component of greater solubility under conditions to displace at least a portion of said component oi lesser solubility, and maintaining in both said contact zones substantially the same temperature.

2. The process of claim 1 wherein said tempergture is above the dew temperature of said re- 3. The process of claim 1 wherein said temperature is between about 5 and 25 C. above the dew point of said reflux.

4. The process according to claim 1 wherein said components are isomers.

5. The process according to claim 1 wherein said reflux is mixed with said solvent prior to returning it to said first contact zone.

6. The process according to claim 1 wherein said reflux passes back to said extraction system independently of said solvent, whereby solvent vapors are prevented from passing overhead.

'1. In a process for fractionating a relatively narrow boiling vapor mixture comprising components ofgreater and lesser solubility in a selective liquid solvent, the steps comprising contacting said mixture in the vapor phase with said liquid solvent in a first contact zone wherein said solvent dissolves preferentially at least a portion of said component of greater solubility as well as the lesser portion of said component of lesser solubility, under conditions to take overhead undissolved vapors, condensing at least a portion of said overhead vapors, returning con- 49 densed vapors to said extraction system as re zones substantial! o a portion flux, passing the resulting solvent through a second contact zone wherein it is contacted with substantially pure vapors of said component of greater solubility, said pure vapors being employed in an amount sufficient to displace at least a portion or said component of lesser solubility and not greater than will completely dissolve in said solvent under the conditions of the process, and maintaining in both said reaction the same temperature above the dew point of said reflux.

8. In a process for fractionatinga relatively narrow boiling mixture of substances of diflerent degrees of saturation, the more saturated substances being less soluble in a selective liquid solvent than the less saturated substances, the steps comprising contacting said mixture in the vapor phase with said liquid solvent in a first contact zone wherein said solvent dissolves preferentially at least a portion of said substance of less saturation as well as the lesser portion of said more saturated substance, under conditions to take overhead undissolved vapors, condensing at least a portion of said overhead vapors, and returning condensed vapors to said extraction system as reflux, passing the resulting solvent through a second contact zone wherein it is contacted with substantially pure vapors of said substance Of less saturation, under conditions to displace at least of said more saturated substance, and maintaining in both said reaction zones substantially the same temperature above the dew temperature of said reflux.

9. A process according to claim 8 wherein said temperature is maintained at a, level corresponding to the maximum volatility ratio of said substances in the presence of said solvent.

10. The process according to claim 8 in which said pure vapors are employed in an amount sufficient to displace at least a portion of said more saturated substance and not greater than will completely dissolve under the conditions of the process.

11. In a process for fractionating a, mixture of butadiene and butylenes, the steps comprising contacting said mixture in the vapor phase with a liquid selective solvent for one of the components of said mixture in a first contact zone wherein said liquid solvent dissolves preferential- 1y at least a portion of the more soluble component as well as a lesser portion of the less so]- uble component, under conditions to take overhead undissolved vapors, condensing at least a portion of said overhead vapors and returning condensed vapors to said extraction system as reflux, passing theresulting liquid solvent through a second contact zone wherein it is contacted with substantially pure vapors of said more soluble component under conditions to displace at least a portion of said less soluble component and maintaining in both said contact zones substantially the same temperature above the dew point of said reflux.

12. In a. process for fractionating a mixture of butadiene and butylenes, the steps comprising contacting said mixture in the vapor phase with a liquid selective solvent for butadiene in a first contact zone wherein said liquid solvent dissolves preferentially at least a portion or said butadiene, as well as a lesser portion 01' said butylene, under conditions to take overhead undissolved vapors, condensing at least a portion of said overhead vapors, and returning condensed vapors to said extraction system as reflux,'passing the resulting liquid solvent through a second contact zone wherein it is contacted with substantially pure vapors of butadiene under conditions to displace at least a portion of said butylenes and maintaining in both said contact zones substantially the same temperature above the dew point of said reflux.

13. In a continuously regenerative process for fractionating a relatively narrow boiling vapor mixture comprising components or greater and lesser solubility in a selective liquid solvent, the steps comprising contacting said mixture in the vapor phase with said lean liquid solvent in a first contact zone wherein said solvent dissolves preferentially at least a portion or said component of greater solubility as well as a smaller portion of said component of lesser solubility under conditions to take overhead undissolved vapors, condensing at least a portion or said overhead vapors and returning condensed vapors to said extraction system as reflux, passing the resulting solvent through a second contact zone wherein it is contacted. with an amount of substantially pure vapors or said component of greater solubility, said amount being suflicient to displace at least a major portion of said component of lesser solubility, and not more than will dissolve substantially completely in said solvent under the conditions oi the process, thereby forming a fat solvent, maintaining in both said reaction zones substantially the same temperature above the dew point of said reflux, stripping ing component of lesser said fat solvent in a distillation zone to produce lean solvent and substantially pure vapors of said component of greater solubility, returning said lean solvent to said first contact zone, and dividing said pure vapor into two portions, one of which is returned to said second contact zone to effect said displacement of said remaining component of lesser solubility and another portion which is withdrawn.

14. In a continuously regenerative process for fractionating a relatively narrow boiling vapor mixture comprising components of greater and lesser solubility in a selective liquid solvent, the steps comprising introducing said mixture in the vapor phase into a first contact zone, introducing said solvent into said contact zone under conditions to dissolve preferentially at least a portion of said component of greater solubility as well as a smaller portion of said component of lesser solubility, under conditions to take overhead undissolved vapors, condensing at least a portion of said overhead vapors, and returning condensed vapors to said extraction system, passing the resulting solvent through a second contact zone, introducing into said second contact zone an amount of substantially pure vapors of said component o1 greater solubility, contacting said solvent with said pure vapors, said amount of pure vapors being sufilcient to displace at least a maior portion of said component of lesser solubility, and not more than will dissolve substantially completely in said solvent, thereby forming a fat solvent, controlling the temperatures of said solvent in said mixture and said vapors at their respective points of introduction, so as to maintain both said contact zones at substantially the same temperature above the dew point of said reflux, stripping said fat solvent in a distillation zone, to produce lean solvent and substantially pure vapors of said component of greater solubility, returning said lean solvent to said first contact zone and dividing said pure vapors into two portions, one of which is returned to said second contact zone to eil'ect said displacement of said remainsolubility and another portion, which is withdrawn.

15. In a process for fractionating a relatively narrow boiling vapor mixture comprising component of greater and lesser solubility in a selective liquid solvent, the steps comprising contacting said mixture in the vapor phase with said liquid solvent in a first contact zone wherein said solvent dissolves preferentially at least a portion or said component of greater solubility as well as a lesser portion or said component of lesser solubili under conditions to talre overhead undissolved vapors, condensing at least a portion of said overhead vapors, and returning condensed vapors to said-extraction system as reflux, passing the resulting solvent through a second contact zone wherein it is contacted with substantially pure vapors of said component of greater solubility under conditions to displace at least a portion of said component of lesser solubility, and circulating a single heat convection medium in indirect heat exchange relation with both said zones to maintain a substantially uniform temperature in the zones above the dew point of said retiux.

THEODORE W. EVANS. RUPERT (L-MORRIS. 

